Methods for forming a silicon nitride film on a substrate and related semiconductor device structures

ABSTRACT

A method for forming a silicon nitride film on a substrate is disclosed. The method may include; forming a cyclical silicon nitride film on the substrate by a cyclical deposition process, wherein the cyclical deposition process comprises at least one of; contacting the substrate with a first reactant comprising a silicon halide source and contacting the substrate with a second reactant comprising a nitrogen source. The method may also include exposing the cyclical silicon nitride film to a plasma. Semiconductor device structures comprising a silicon nitride film are also disclosed.

FIELD OF INVENTION

The present disclosure generally relates to methods for forming a silicon nitride film on a substrate and related semiconductor device structures including a silicon nitride film.

BACKGROUND OF THE DISCLOSURE

In the field of semiconductor device technology silicon nitride films may be utilized during the fabrication of semiconductor integrated circuitry. For example, silicon nitride films may be utilized as an insulating material during the fabrication of semiconductor device structures, such as, for example, transistors, memory cells, logic devices, memory arrays, etc.

There is a need in the field of semiconductor device technology for low temperature deposition processes for high quality silicon nitride films; such low temperature deposition processes should also provide precise control of the film thickness, thickness uniformity and conformality.

Common silicon nitride film deposition processes require high temperature deposition, i.e., around 600° C. to 800° C., to attain the reaction between precursors such as dichlorosilane (DCS) and ammonia (NH₃). State of the art device structures may not be able to withstand such a high thermal budget which may further result in a deterioration of device performance and may cause device integration problems.

An alternative solution to high temperature deposition processes may be to utilize a plasma to activate the precursors which may in turn allow for low temperature reactions and reduced deposition temperatures for silicon nitride films. However, plasma based deposition processes may be limited in deposition performance, i.e., step coverage, uniformity of film quality achievable for high aspect ratio structures and plasma based deposition processes may damage the underlying device structures. Therefore low temperature deposition processes for silicon nitride films and semiconductor device structures including such silicon nitride films may be needed to improve semiconductor device performance.

SUMMARY OF THE DISCLOSURE

In accordance with at least one embodiment of the disclosure, a method for forming a silicon nitride film a on a substrate is provided. The method may comprise; forming a cyclical silicon nitride film on the substrate by a cyclical deposition process, wherein the cyclical deposition process comprises at least one cycle of, contacting the substrate with a first reactant comprising a silicon halide source, and contacting the substrate with a second reactant comprising a nitrogen source. The method provided may also comprise exposing the cyclical silicon nitride film to a plasma.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

While the specification concludes with claims particularly pointing out and distinctly claiming what are regarded as embodiments of the invention, the advantages of embodiments of the disclosure may be more readily ascertained from the description of certain examples of the embodiments of the disclosure when read in conjunction with the accompanying drawing, in which:

FIG. 1 illustrates a process flow diagram illustrating an exemplary deposition method in accordance with embodiments of the disclosure;

FIG. 2 illustrates wet etch rates (WER) for silicon nitride films formed by embodiments of the disclosure;

FIG. 3 illustrates ellipsometry data demonstrating the substrate bow induced by silicon nitride films formed by the embodiments of the disclosure;

FIG. 4 illustrates Rutherford backscattering data for “as-deposited” silicon nitride films and silicon nitride films formed by the embodiments of the disclosure;

FIG. 5 illustrates Fourier Transform Infrared spectroscopy data for an “as-deposited” silicon nitride film and from silicon nitride films formed by the embodiments of the disclosure;

FIG. 6 illustrates a Scanning Electron Microscope images of a silicon substrate with a conformal silicon nitride film formed thereon;

FIG. 7 illustrates a schematic diagram of an example semiconductor device structure including a silicon nitride film formed by the embodiments of the disclosure;

FIG. 8 illustrates a schematic diagram of a reaction system configured for performing the embodiments of the disclosure.

It will be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of illustrated embodiments of the present disclosure.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Although certain embodiments and examples are disclosed below, it will be understood by those in the art that the invention extends beyond the specifically disclosed embodiments and/or uses of the invention and obvious modifications and equivalents thereof. Thus, it is intended that the scope of the invention disclosed should not be limited by the particular disclosed embodiments described below.

As used herein, the term “substrate” may refer to any underlying material or materials that may be used, or upon which, a device, a circuit or a film may be formed.

As used herein, the term “cyclical deposition” may refer to the sequential introduction of precursors (reactants) into a reaction chamber to deposit a layer over a substrate and includes processing techniques such as atomic layer deposition and cyclical chemical vapor deposition.

As used herein, the term “atomic layer deposition” (ALD) may refer to a vapor deposition process in which deposition cycles, preferably a plurality of consecutive deposition cycles, are conducted in a process chamber. Typically, during each cycle the precursor is chemisorbed to a deposition surface (e.g., a substrate surface or a previously deposited underlying surface such as material from a previous ALD cycle), forming a monolayer or sub-monolayer that does not readily react with additional precursor (i.e., a self-limiting reaction). Thereafter, if necessary, a reactant (e.g., another precursor or reaction gas) may subsequently be introduced into the process chamber for use in converting the chemisorbed precursor to the desired material on the deposition surface. Typically, this reactant is capable of further reaction with the precursor. Further, purging steps may also be utilized during each cycle to remove excess precursor from the process chamber and/or remove excess reactant and/or reaction byproducts from the process chamber after conversion of the chemisorbed precursor. Further, the term “atomic layer deposition,” as used herein, is also meant to include processes designated by related terms such as, “chemical vapor atomic layer deposition”, “atomic layer epitaxy” (ALE), molecular beam epitaxy (MBE), gas source MBE, or organometallic MBE, and chemical beam epitaxy when performed with alternating pulses of precursor composition(s), reactive gas, and purge (e.g., inert carrier) gas.

As used herein, the term “cyclical chemical vapor deposition” may refer to any process wherein a substrate is sequentially exposed to two or more volatile precursors, which react and/or decompose on a substrate to produce a desired deposition.

As used herein, the term “substrate” may refer to any underlying material or materials that may be used, or upon which a device, a circuit or a film may be formed. Substrate may comprise a wafer, such as a silicon wafer, a glass substrate or any other type of substrate.

The embodiments of the disclosure may include methods for forming a silicon nitride film on a substrate and particularly for forming a high quality silicon nitride film on a substrate at reduced deposition temperatures. As a non-limiting example embodiment of the disclosure a method of forming a silicon nitride film on a substrate may include a number of complete deposition cycles, wherein each complete deposition cycle includes depositing a cyclical silicon nitride film to a desired thickness and then exposing the cyclical silicon nitride film to a plasma. Embodiments of the disclosure have shown that exposing the cyclical silicon nitride film to a plasma improves the properties of the cyclical silicon nitride films, such as, for example, improving the wet etch rate of the plasma treated silicon nitride film formed. A number of complete deposition cycles, i.e., cyclical silicon nitride deposition and plasma exposures, may be performed to deposit a high quality silicon nitride film with improved qualities.

The methods of the disclosure may be understood with reference to FIG. 1 which illustrates a non-limiting example embodiment of a method for forming a silicon nitride film on a substrate. For example, FIG. 1 may illustrate a method 100 for forming a silicon nitride film on a substrate by a two or more complete deposition cycles. The method 100 may comprise a first process in the complete deposition cycle comprising process block 102 which may comprise a cyclical deposition process for forming a cyclical silicon nitride film on a substrate. In more detail the cyclical deposition process for forming a cyclical silicon nitride may comprise an atomic layer deposition process or alternatively may comprise a cyclical chemical vapor deposition process. A non-limiting example embodiment of a cyclical deposition process may include ALD, wherein ALD is based on typically self-limiting reactions, whereby sequential and alternating pulses of reactants are used to deposit about one atomic (or molecular) monolayer of material per deposition cycle. The deposition conditions and precursors are typically selected to provide self-saturating reactions, such that an adsorbed layer of one reactant leaves a surface termination that is non-reactive with the gas phase reactants of the same reactant. The substrate is subsequently contacted with a different reactant that reacts with the previous termination to enable continued deposition. Thus, each cycle of alternated pulses typically leaves no more than about one monolayer of the desired material. However, as mentioned above, the skilled artisan will recognize that in one or more ALD cycles more than one monolayer of material may be deposited, for example if some gas phase reactions occur despite the alternating nature of the process.

In an ALD-type process for depositing a cyclical silicon nitride film, one ALD cycle may comprise exposing the substrate to a first reactant, as illustrated in process block 104 of FIG. 1, removing any unreacted first reactant and reaction byproducts from the reaction space and exposing the substrate to a second reactant, as illustrated by process block 106 of FIG. 1, followed by a second removal step. The first reactant may comprise a silicon halide source and the second reactant may comprise a nitrogen source.

Precursors may be separated by inert gases, such as argon (Ar) or nitrogen (N₂), to prevent gas-phase reactions between reactants and enable self-saturating surface reactions. In some embodiments, however, the substrate may be moved to separately contact a first vapor phase reactant and a second vapor phase reactant. Because the reactions self-saturate, strict temperature control of the substrates and precise dosage control of the precursors is not usually required. However, the substrate temperature is preferably such that an incident gas species does not condense into monolayers or multimonolayers nor thermally decompose on the surface. Surplus chemicals and reaction byproducts, if any, are removed from the substrate surface, such as by purging the reaction space or by moving the substrate, before the substrate is contacted with the next reactive chemical. Undesired gaseous molecules can be effectively expelled from a reaction space with the help of an inert purging gas. A vacuum pump may be used to assist in the purging.

Reactors capable of being used to grow cyclical silicon nitride films can be used for the deposition. Such reactors include ALD reactors, as well as CVD reactors equipped with appropriate equipment and means for providing the precursors. According to some embodiments, a showerhead reactor may be used.

Examples of suitable reactors that may be used include commercially available single substrate (or single wafer) deposition equipment such as Pulsar® reactors (such as the Pulsar® 2000 and the Pulsar® 3000 and Pulsar® XP ALD), and EmerALD® XP and the EmerALD® reactors, available from ASM America, Inc. of Phoenix, Ariz. and ASM Europe B.V., Almere, Netherlands. Other commercially available reactors include those from ASM Japan K.K. (Tokyo, Japan) under the tradename Eagle® XP and XP8. In some embodiments the reactor is a spatial ALD reactor, in which the substrates moves or rotates during processing.

In some embodiments a batch reactor may be used. Suitable batch reactors include, but are not limited to, Advance® 400 Series reactors commercially available from ASM Europe B.V (Almere, Netherlands) under the trade names A400 and A412 PLUS. In some embodiments a vertical batch reactor is utilized in which the boat rotates during processing, such as the A412. Thus, in some embodiments the wafers rotate during processing. In other embodiments, the batch reactor comprises a minibatch reactor configured to accommodate 10 or fewer wafers, 8 or fewer wafers, 6 or fewer wafers, 4 or fewer wafers, or 2 wafers. In some embodiments in which a batch reactor is used, wafer-to-wafer uniformity is less than 3% (1 sigma), less than 2%, less than 1% or even less than 0.5%.

The deposition processes described herein can optionally be carried out in a reactor or reaction space connected to a cluster tool. In a cluster tool, because each reaction chamber is dedicated to one type of process, the temperature of the reaction chamber in each module can be kept constant, which improves the throughput compared to a reactor in which the substrate is heated up to the process temperature before each run. Additionally, in a cluster tool it is possible to reduce the time to pump the reaction chamber to the desired process pressure levels between substrates.

A stand-alone reactor can be equipped with a load-lock. In that case, it is not necessary to cool down the reaction space between each run. In some embodiments a deposition process for depositing a thin cyclical silicon nitride film may comprise a plurality of ALD cycles.

In some embodiments the cyclical deposition processes are used to form a cyclical silicon nitride film on a substrate and the cyclical deposition process may be an ALD type process. In some embodiments the cyclical deposition may be a hybrid ALD/CVD or cyclical CVD process. For example, in some embodiments the growth rate of the ALD process may be low compared with a CVD process. One approach to increase the growth rate may be that of operating at a higher substrate temperature than that typically employed in an ALD process, resulting in a chemical vapor deposition process, but still taking advantage of the sequential introduction of precursors, such a process may be referred to as cyclical CVD.

According to some embodiments, ALD processes are used to form a cyclical silicon nitride film on a substrate, such as an integrated circuit workpiece. In some embodiments of the disclosure each ALD cycle comprises two distinct deposition steps or phases.

In a first phase of the cyclical deposition (“the silicon phase”), the substrate surface on which deposition is desired is contacted with a first vapor phase reactant (process block 104 of FIG. 1) comprising a silicon precursor which chemisorbs onto the substrate surface, forming no more than about one monolayer of reactant species on the surface of the substrate. It should be appreciated that in some embodiments, each contacting step may be repeated one or more times prior to advancing on to the subsequent processing step, i.e., prior to a subsequent contacting step or removal/purge step.

In some embodiments, a silicon precursor, also referred to herein as the “silicon compound” may comprise a silicon halide source. In some embodiments, the first reactant may comprise a silicon halide source and may further comprise at least one of silicon tetraiodide (SiI₄), silicon tetrabromide (SiBr₄), silicon tetrachloride (SiCl₄), hexachlorodisilane (Si₂Cl₆), hexaiododisilane (Si₂I₆), octoiodotrisilane (Si₃I₈). In embodiments wherein the silicon halide source comprises silicon tetraiodide (SiI₄) the silicon tetraiodide source may be preheated to provide sufficient vapor pressure for delivery to the reaction chamber, for example, in some embodiments the silicon tetraiodide precursor source may be preheated to a temperature of between approximately 90° C. and approximately 125° C., or in some embodiments the silicon tetraiodide may be preheated to a temperature of approximately 100° C.

In some embodiments, exposing the substrate to a silicon halide source may comprise pulsing the silicon precursor (e.g., the silicon tetraiodide (SiI₄)) over the substrate for a time period of between about 0.5 seconds and about 30 seconds, or between about 0.5 seconds and about 10.0 seconds, or between about 0.5 seconds and about 5.0 seconds. In addition, during the pulsing of the silicon halide source over the substrate the flow rate of the silicon halide source may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 250 sccm or even less than 100 sccm.

Excess silicon halide source and reaction byproducts (if any) may be removed from the substrate surface, e.g., by purging with an inert gas. For example, in some embodiments of the disclosure the methods may include a purge cycle wherein the substrate surface is purged for a time period of less than approximately 5.0 seconds. Excess silicon halide source and any reaction byproducts may be removed with the aid of a vacuum generated by a pumping system.

In a second phase of the cyclical deposition, e.g., an ALD cycle (“the nitrogen phase”), the substrate is contacted with a second vapor phase reactant comprising a nitrogen source (process block 106 of FIG. 1). In some embodiments of the disclosure, methods may further comprise selecting the nitrogen source to comprise at least one of ammonia (NH₃), hydrazine (N₂H₄) or an alkyl-hydrazine, wherein the alkyl-hydrazine may refer to a derivative of hydrazine which may comprise an alkyl functional group and may also comprise additional functional groups, non-limiting example embodiments of an alkyl-hydrazine may comprise at least one of tertbutylhydrazine (C₄H₉N₂H₃), methylhydrazine (CH₃NHNH₂) or dimethylhydrazine ((CH₃)₂N₂H₂).

In some embodiments, exposing the substrate to the nitrogen source may comprise pulsing the nitrogen source (e.g., ammonia (NH₃)) over the substrate for a time period of between about 0.5 seconds to about 30.0 seconds, or between about 0.5 seconds to about 10 seconds, or between about 0.5 second to about 5 seconds. During the pulsing of the nitrogen source over the substrate the flow rate of the nitrogen source may be less than 4000 sccm, or less than 2000 sccm, or less than 1000 sccm, or even less than 250 sccm.

The second vapor phase reactant comprising a nitrogen source may react with silicon-containing molecules left on the substrate surface. In some embodiments, the second phase nitrogen source may react with the silicon-containing molecules left on the substrate surface to deposit a cyclical silicon nitride film.

Excess second source chemical and reaction byproducts, if any, may be removed from the substrate surface, for example by a purging gas pulse and/or vacuum generated by a pumping system. Purging gas is preferably any inert gas, such as, without limitation, argon (Ar), nitrogen (N₂) or helium (He). A phase is generally considered to immediately follow another phase if a purge (i.e., purging gas pulse) or other reactant removal step intervenes.

Although as illustrated in method 100 of FIG. 1, the cyclical deposition process 102 may comprise contacting the substrate with a first reactant 104 followed subsequently by contacting the substrate with a second reactant 106 it should be appreciated that embodiments of the disclosure may reverse the contacting sequence and the substrate may be first contacted with the second reactant 106 subsequently followed by contacting the substrate with the first reactant 104. It should also be appreciated that the substrate may be contacted multiple times with the first reactant prior to contacting the substrate with the second reactant and vice versa.

Embodiments of the disclosure may further comprise heating the substrate during the cyclical deposition process 102, e.g., heating the substrate during the ALD process for depositing a cyclical silicon nitride film on the substrate. In some embodiments method may comprise heating the substrate to a temperature of approximately less than 200° C., or to a temperature of less than approximately 250° C., or to a temperature of less than approximately 300° C., or to a temperature of less than approximately 350° C., or to a temperature of less than approximately 400° C., or to a temperature of less than approximately 450° C., or even to a temperature of less than approximately 500° C.

Embodiments of the disclosure may further comprise reducing the pressure in the reaction chamber utilized for depositing the cyclical silicon nitride by a cyclical deposition process. For example, in some embodiments the cyclical deposition may be performed at a reaction chamber pressure of less than 50 Torr, or at a reaction chamber pressure of less than 25 Torr, or at a reaction chamber pressure of less than 10 Torr, or even at a reaction chamber pressure of less than 5 Torr.

The deposition rate of the cyclical silicon nitride film by the cyclical deposition process, e.g., an ALD type process, which is typically presented as A/pulsing cycle, depends on a number of factors including, for example, on the number of available reactive surface sites or active sites on the surface and bulkiness of the chemisorbing molecules. In some embodiments, the deposition rate of such films may range from about 0.1 to about 5.0 Å/pulsing cycle. In some embodiments, the deposition rate can be about 0.1, 0.2, 0.3, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 Å/pulsing cycle.

The cyclical deposition process for forming a cyclical silicon nitride film on the substrate may be repeated one or more times until the desired thickness of the cyclical silicon nitride is achieved. Referring to FIG. 1 process block 108 illustrates a decision gate for determining if the cyclical deposition process should or should not be repeated, the decision gate being determined by the desired thickness of the cyclical silicon nitride film. For example, in some embodiments forming the cyclical silicon nitride film on the substrate by the cyclical deposition process comprises forming the cyclical silicon nitride film with a thickness of between approximately 5 Angstroms and approximately 30 Angstroms. In some embodiments the methods may comprise forming the cyclical silicon nitride film on the substrate with a thickness of less than 50 Angstroms, or less than 40 Angstroms, or less than 30 Angstroms, or less than 20 Angstroms, or even less than 10 Angstroms. In some embodiments the methods may comprise forming the cyclical silicon nitride film on the substrate by the cyclical deposition process with a thickness of approximately 15 Angstroms.

In further embodiments of the disclosure the cyclical silicon nitride may be formed to a greater thickness, for example, if the underlying substrate comprises fragile device structures or partially fabricated fragile device structures, then the cyclical silicon nitride may be increased in thickness to protect the fragile materials from subsequent plasma processes, in such embodiments the cyclical silicon nitride film may have a thickness of greater than 5 nm, or greater than 10 nm, or even greater than 25 nm.

Once the desired thickness of the cyclical silicon nitride film is obtained the cyclical silicon nitride film may be exposed to a plasma in order to improve the materials characteristics of the deposited cyclical silicon nitride film, i.e., such as improving the wet etch rate of the silicon nitride film deposited. Therefore methods of the disclosure may comprise exposing the cyclical silicon nitride to a plasma, as illustrate by process block 110 of FIG. 1. In more detail, once the desired thickness of the cyclical silicon nitride film has been obtained the substrate may be transferred to another reaction chamber configured for exposing the substrate and particular the cyclical silicon nitride film, to a plasma, i.e., a plasma treatment. In some embodiments the same reaction chamber may be utilized for both the cyclical deposition of the cyclical silicon nitride film and the exposing of the cyclical silicon nitride film to a plasma. In alternative embodiments, the reaction chamber for the cyclical deposition of the cyclical silicon nitride film and the reaction chamber for exposing the cyclical silicon nitride film to a plasma may be different from one another. In embodiments where different reaction chambers are utilized for the cyclical deposition process and the plasma treatment process, the substrate and the overlying cyclical silicon nitride film may be transferred from a first reaction chamber (for the cyclical silicon nitride film deposition) to a second reaction chamber (for the plasma treatment) without exposure to the ambient atmosphere. In other words, methods of the disclosure may comprise forming the cyclical silicon nitride film on the substrate by a cyclical deposition process and exposing the cyclical silicon nitride film to a plasma utilizing the same semiconductor processing apparatus. The semiconductor processing apparatus utilized for the cyclical deposition and the plasma treatment may comprise a cluster tool which comprises two or more reaction chambers and which may further comprise a transfer chamber through which the substrate maybe transported between the first reaction chamber and the second reaction chamber. In some embodiments, the environment within the transfer chamber may be control, i.e., the temperature, pressure and ambient gas, such that the substrate and particularly the cyclical silicon nitride are not exposed to the ambient atmosphere. In some embodiments the reaction chamber configured for exposing the cyclical silicon nitride film to a plasma may be configured with a capacitively coupled plasma (CCP) source, an inductively coupled plasma (ICP) source or a remote plasma (RP) source.

Once the substrate and the associated overlying cyclical silicon nitride film are positioned in an appropriate reaction chamber configured for a plasma treatment, the methods of the disclosure may comprise exposing the cyclical silicon nitride film to a plasma. In some embodiments, the source gas from which the plasma is generated may comprise one or more of nitrogen (N₂), helium (He), hydrogen (H₂) and argon (Ar). In particular embodiments of the disclosure the source gas from which the plasma is generated may comprise a mixture of helium (He) and nitrogen (N₂) and the proportion of helium (He) gas to nitrogen (N₂) gas may be equal, i.e. 50% helium gas (He) to 50% nitrogen gas (N₂) (50:50). In alternate embodiments, the proportion of helium (He) gas to nitrogen (N₂) may be 10%:90%, or 20%:80%, or 30%:70%, or 40%:60%, or 60%:40%, or 70%:30%, or 80%:20%, or even 90%:10%.

In some embodiments of the disclosure, exposing the cyclical silicon nitride film to a plasma may comprise applying a power to the plasma source gas(es) of greater than approximately 150 W, or greater than 300 W, or greater than 600 W, or even greater than 900 W. In addition the reaction chamber for exposing the cyclical silicon nitride film to a plasma may be operated at a reduced pressure, for example, in some embodiments the reaction chamber for exposing the cyclical silicon nitride to a plasma may operate at a pressure of approximately less than 4 Torr, or may operate at a pressure of approximately less 2 Torr, or may even operate at a pressure of approximately 1 Torr. In some embodiments, the substrate may be heated during the plasma treatment process, for example, exposing the cyclical silicon nitride film to a plasma may comprise heating the substrate and the associated cyclical silicon nitride film to a temperature of greater than approximately 100° C., or to a temperature of greater than approximately 200° C., or even to a temperature of greater than approximately 250° C.

In some embodiments of the disclosure, exposing the cyclical silicon nitride film to a plasma comprises exposing the cyclical silicon nitride to a plasma for a time period of less than approximately 300 second, or for a time period of less than 150 seconds or even for a time period of less than 90 seconds. In certain embodiments of the disclosure the cyclical silicon nitride may be exposed to the plasma treatment for longer period of time, for example, for a time period greater than 2 minutes, or greater than 5 minutes, or even greater than 10 minutes. It should be noted that the longer the substrate and the associated cyclical silicon nitride film are exposed to the plasma the more likely that the beneficial effects of the plasma treatment are to saturate and very long plasma exposure times may even result in damage to the cyclical silicon nitride surface.

As a non-limiting example embodiment of the disclosure, exposing the cyclical silicon nitride film to a plasma may comprise a helium (He) and nitrogen (N₂) (50%:50%) gas plasma in a reaction chamber comprising a capacitively coupled plasma (CCP) source with a plasma power of 600 W, a reaction chamber pressure of 2 Torr for a time period of 90 seconds.

After exposing the cyclical silicon nitride to a plasma, one complete deposition cycle has been performed, a single complete deposition cycle therefore comprising forming the cyclical silicon nitride film on the substrate by a cyclical deposition process and exposing the cyclical silicon nitride film to a plasma. The embodiments of the disclosure may comprise repeating the complete deposition cycle two or more times. For example, upon completion of a first complete deposition cycle, i.e., upon completion of the plasma treatment of the cyclical silicon nitride, the method 100 of FIG. 1 may proceed with decision gate 112 wherein the decision to proceed with another complete deposition cycle is based on the thickness of the silicon nitride film achieved. In embodiments wherein decision gate 112 (of FIG. 1) results in the decision to repeat the complete deposition cycle one or more times, the substrate and the overlying silicon nitride film may be returned (i.e., transferred) to a reaction chamber configured for cyclical deposition 102, e.g., a reaction chamber configured for ALD type processes. As previously described the substrate may be transferred from the plasma treatment reaction chamber to the cyclical deposition reaction chamber without exposure of the substrate to the ambient atmosphere, such a transfer of the substrate maybe achieved utilizing a cluster tool comprising a transfer chamber with controlled environmental conditions.

Although the complete deposition cycle illustrated by method 100 in FIG. 1 illustrates a cyclical deposition cycle 102 followed subsequently by exposing the substrate to a plasma 110, it may be appreciated that embodiments of the disclosure may also include methods wherein the substrate is first exposed to a plasma treatment 110 prior to performing the cyclical deposition cycle 102, in other words methods of the embodiments may further comprise exposing the substrate to a plasma prior to forming a cyclical silicon nitride film on a substrate by a cyclical deposition cycle. Not to be bound by theory but it is believed that a pretreatment which comprises exposing the substrate to a plasma treatment prior to a cyclical silicon nitride deposition may improve the cyclical silicon nitride deposition process by altering the surface energy of the substrate upon which the cyclical silicon nitride film is to be deposited and thereby improving the cyclical silicon nitride film nucleation. In some embodiments of the disclosure the plasma pretreatment of the substrate may comprise one or more of a nitrogen (N₂), helium (He), Argon, or Nitrogen/Helium (e.g. 50%/50%) plasma chemistry, performed at a reaction chamber pressure of between approximately 0.5 Torr to approximately 4 Torr, at a plasma power of approximately 600 W, for a time period of between approximately 10 second and approximately 90 seconds. It should be also be appreciated that a number of plasma treatments may be performed in a single complete deposition cycle as a well as a number of cyclical deposition cycles 102 may be performed during a single deposition cycle.

In further embodiments each complete deposition cycle may differ from the proceeding and/or the subsequent complete deposition cycle or alternatively each deposition cycle may comprise the same process parameters. In embodiments wherein two or all of the complete deposition cycles differ from one another the process parameters for one or all of the processes comprising the cyclical silicon nitride film deposition and the plasma treatment may be altered between each complete deposition cycle. As a non-limiting example, in some embodiments the underlying substrate may comprise fragile device structures or fragile partially fabricated device structure and therefore an initial cyclical silicon nitride film may be deposited to a greater a thickness to ensure protection of the fragile materials during the subsequent plasma treatment.

In some embodiments of the disclosure the complete deposition cycle may be repeated more than two times, or more than five times, or more than ten times, or even more than twenty times. In some embodiments the complete deposition cycle may be repeated until a silicon nitride layer with a thickness of greater than approximately 5 nm, or greater than approximately 10 nm, or even greater than approximately 25 nm. The silicon nitride film depositing utilizing one or more complete deposition cycles of the current disclosure may have improved thickness non-uniformity, wherein the silicon nitride film deposited has a thickness non-uniformity of less than 15% 1-sigma, or less than 10% 1-sigma, or less than 5% 1-sigma, or even less than 2% 1-sigma.

Once a silicon nitride film of a desired thickness has been deposited utilizing a number of complete deposition cycles (as illustrated in FIG. 1) the substrate and the associated silicon nitride film formed thereon may be removed from the semiconductor processing apparatus. However, prior to removing the silicon nitride film from the semiconductor processing apparatus the silicon nitride film may undergo further processing. For example, exposing the cyclical silicon nitride to a plasma may have beneficial effects as described herein, however the plasma treatment of the cyclical silicon nitride surface may render such a surface highly reactive and therefore the deposited silicon nitride may require a passivation process prior to exposure to ambient conditions to substantially prevent oxidation processes from occurring. Therefore in some embodiments of the disclosure upon completion of the final complete deposition cycle methods may comprise contacting the silicon nitride film with a nitrogen precursor prior to removing the silicon nitride film from a semiconductor processing apparatus. Further embodiments of the disclosure may comprise selecting the nitrogen precursor to comprise at least one of ammonia or nitrogen (N₂) plasma, e.g., a low power remote plasma treatment. In some embodiments the silicon nitride film may be exposed to the nitrogen precursor of a time period between approximately 5 seconds and approximately 60 seconds to ensure passivation of the silicon nitride surface.

The high quality of the silicon nitride films deposited by the embodiments of the disclosure herein may be determined in a number of ways. For example, the silicon nitride films deposited by the embodiments disclosed herein may be subjected to a wet chemical etch process to determine the wet etch rate (WER) of the deposited silicon nitride film. As a non-limiting example, a silicon nitride film formed by two or more complete deposition cycles of method 100 (of FIG. 1) may have a WER in a solution of 2000:1 water (H₂O) to hydrofluoric acid (HF) of approximately less than 5 Angstroms/minute. As a comparison a silicon nitride film deposited without utilizing the methods described herein exhibited a WER in a solution of 2000:1 water (H₂O) to hydrofluoric acid (HF) of 60 Angstroms/minute, therefore the embodiments described herein are capable of depositing a silicon nitride film with approximately twelve (12) times more resistance to wet chemical etching in comparison to silicon nitride films formed by alternative methods.

As a further non-limiting example embodiment, FIG. 2 illustrates the WER in 2000:1 (H₂O:HF) for silicon nitride films formed by the embodiments described herein utilizing different plasma source gases for the plasma treatment process. The WER data for a silicon nitride film deposited and plasma treated utilizing plasma source gases comprising hydrogen (H₂) and nitrogen (N₂) (50%:50%) is labelled as 200 and demonstrates a WER of between approximately 35 Angstroms/min and approximately 32 Angstroms/min. The WER data for a silicon nitride film deposited and plasma treated utilizing plasma source gases comprising helium (He) and nitrogen (N₂) (50%:50%) is labelled as 202 and demonstrates a WER of between approximately 12 Angstroms/min and approximately 3 Angstroms/min.

In some embodiments the methods of the disclosure may also be utilized to alter the stress in the deposited silicon nitride film and the resulting bow in the underlying substrate. For example, the methods of the disclosure may utilize differing numbers of complete deposition cycles for the formation of a silicon nitride layer, the number of deposition cycles and particularly the frequency of plasma treatments having a direct effect on the stress in the deposited silicon nitride film and the resulting bow in the substrate.

TABLE 1 Plasma Center Treatment Thickness Non-uniform Average WER Frequency (Angstroms) %-1 sigma Stress (MPa) Angstroms/min As deposited 93.0 5.0 590 60 2X 97.6 4.5 −36 12 3X 90.2 2.5 −264 8 4X 85.4 1.6 −584 5 7X 86.1 6.4 −1034 6

Table 1 illustrates five (5) different silicon nitride films, a control sample deposited by conventional methods without plasma treatments (labelled “As deposited”) and four (4) silicon nitride films nominally deposited to the same thickness, i.e., approximately 90 Angstroms, but with an increasing frequency of plasma treatments. It should be noted that the plasma treatment utilized for acquiring the data in Table 1 comprises a helium (He), nitrogen (N₂) (50%:50%) plasma at a power of 600 W, a reaction chamber pressure of 2 Torr and a plasma exposure time period of ninety (90) seconds. Table 1 clearly demonstrates that the WER of the silicon nitride films improve with increasing the plasma treatment frequency, as previously noted. In addition Table 1 clearly demonstrates that the stress in the deposited silicon nitride films may also be directly controlled utilizing the methods of this disclosure. For example, the “as deposited” silicon nitride film demonstrates a tensile strain of 590 MPa whereas the silicon nitride formed by the embodiments of the disclosure with seven (7) plasma treatment cycles demonstrates a compressive strain of −1034 MPa. Therefore, in some embodiments of the disclosure the exposing of the cyclical silicon nitride to a plasma further comprises altering the stress in the silicon nitride film and may further comprise altering the stress in the silicon nitride film from a tensile state to a compressive state.

As a further non-limiting example of the embodiments of the disclosure FIG. 3 illustrates ellipsometer measurements of the wafer bow induced in the substrate by the stress in the overlying silicon nitride film and demonstrates the stress obtained utilizing various plasma chemistries. The wafer bow in the “as-deposited” silicon nitride sample wafer (labelled 300) demonstrates a tensile stress with a maximum wafer bow of approximately −3 microns. In contrast, a silicon nitride film formed by the embodiments of the disclosure (labelled 302), in particular by exposing the cyclical silicon nitride to a hydrogen (H₂) and nitrogen (N₂) plasma chemistry, results in a compressive stress and a maximum wafer bow of approximately 7 microns. Therefore, embodiments of the disclosure may comprise exposing the cyclical silicon nitride to a plasma and may further comprise altering the degree of bow in the substrate.

In some embodiments of the disclosure, the method of forming a silicon nitride film utilizing a number of complete deposition cycles, including a cyclical silicon nitride deposition and a plasma treatment, may be utilized to alter the composition of the deposited silicon nitride film. For example, FIG. 4 illustrates Rutherford backscattering data collected from six (6) silicon nitride films, the initial four (4) silicon nitride films labelled as data 402, 404, 406 and 408 were “as deposited”, i.e., no plasma treatment was employed, whereas the final two (2) silicon nitride films labelled as data 410 and 412 were formed by the method of the embodiments described herein, i.e., were treated to one or more plasma treatments. The data for the “as-deposited” silicon nitride films demonstrates that as the deposition temperature is increased from 250° C. to 480° C. the atomic percentage of hydrogen (labelled c) decreases and the atomic percentage of silicon (labelled a) and nitrogen (labelled b) increases. Not to be bound by theory but it is believed that excess hydrogen in the silicon nitride film may result in silicon nitride films of poorer quality, i.e., increased WER and poor electrical characteristics. The data for the “as-deposited” silicon nitride films indicates that higher quality silicon nitride films may be formed at higher deposition temperatures, however as previously stated, such high deposition temperatures may be detrimental to state of the art semiconductor device structures. In contrast, the data labelled 410 and 412 demonstrate silicon nitride films formed by the methods of the embodiments described herein and both data 410 and 412 comprise silicon nitride films deposited at the low deposition temperature of 250° C. As seen in FIG. 4, both the H₂—N₂ plasma treated silicon nitride film (data 410) and the He—N₂ plasma treated silicon nitride film (data 412) demonstrate compositions similar to the high temperature silicon nitride films of data 408. Therefore the method described herein allows for low temperature deposition of silicon nitride films with an improved composition, the improved composition resembling that of silicon nitride films deposited at much higher temperatures, for example above 400° C.

Embodiments of the disclosure may comprise forming a silicon nitride film on a substrate whilst heating the substrate to a temperature of less than approximately 250° C., wherein the silicon nitride film on the substrate has an atomic percentage of hydrogen less than 25%, or has an atomic percentage of hydrogen of less than 20%, or has an atomic percentage of hydrogen of less than 15%, or has an atomic percentage of hydrogen of less than 10%, or even has an atomic percentage of hydrogen of less than 5%.

Further embodiments of the disclosure may comprise forming a silicon nitride film on a substrate whilst heating the substrate to a temperature of less than approximately 250° C., wherein the silicon nitride film on the substrate has an atomic percentage of silicon greater than 25%, or has an atomic percentage of silicon of greater than 30%, or has an atomic percentage of silicon greater than 35%, or even has an atomic percentage of silicon greater than 40%.

Further embodiments of the disclosure may comprise forming a silicon nitride film on a substrate whilst heating the substrate to a temperature of less than approximately 250° C., wherein the silicon nitride film on the substrate has an atomic percentage of nitrogen greater than 35%, or has an atomic percentage of nitrogen of greater than 40%, or has an atomic percentage of nitrogen greater than 45%, or has an atomic percentage of nitrogen greater than 50%, or even has an atomic percentage of nitrogen greater than 55%.

As previously described herein, the embodiments of the disclosure may reduce the atomic percentage of hydrogen in the deposited silicon nitride film. In particular the methods described herein may reduce the amount of hydrogen bound to nitrogen, i.e., N—H bonding groups. As a non-limiting example, FIG. 5 illustrates Fourier Transform Infrared Spectroscopy (FTIR) data from an “as-deposited” and from silicon nitride films deposited by the methods described herein. In more detail, the data curve 502 illustrates the FTIR spectroscopy for the “as-deposited” silicon nitride film and clearly indicates the presence of N—H bonds due to the peak in the data corresponding to the N—H bond position. With continued reference to FIG. 5, the data curve 504 illustrates the FTIR spectroscopy for a silicon nitride formed by the methods described herein, and particular was treated to a helium (He), nitrogen (N₂) plasma. The data curve 504 shows no visible peak at the N—H bond position and it is therefore believed that the plasma treatment effectively removes the N—H bonds from the silicon nitride film.

In some embodiments of the disclosure the silicon nitride films formed by the methods described herein may be deposited on three-dimensional structures. As a non-limiting example, FIG. 6 illustrates a scanning electron microscope (SEM) cross section image of a silicon substrate 604 which has been etched such that it comprises surface vias with a depth of approximately 220 nanometers. Deposited over the surface of the etched silicon substrate 604 is a conformal silicon nitride film 602 formed by the embodiments described herein. As demonstrated by the SEM cross section image of FIG. 6 the silicon nitride films formed by the embodiments of the disclosure are conformal to the underlying surface topography. Therefore, in some embodiments the step coverage of the silicon nitride film may be equal to or greater than about 50%, greater than about 80%, greater than about 90%, about 95%, about 98% or about 99% or greater in structures having aspect ratios (height/width) of more than about 2, more than about 5, more than about 10, more than about 25, more than about 50 or more than about 100.

One of skill in the art will recognize that the processes described herein are applicable to many contexts, including the fabrication of semiconductor device structures, such as, but not limited to, memory devices (e.g., resistive memory, DRAM, and VNAND), diodes including light emitting diodes and transistors including planar devices as well as multiple gate transistors, such as FinFETs. As a non-limiting example, the silicon nitride films of the current disclosure may be utilized as useful layers in the fabrication of semiconductor device structures. For example, the silicon nitride films of the current disclosure may be utilized as sacrificial films or hard masks for applications related to multiple patterning processes, such as, for example, double or quadruple patterning applications. For example, the embodiments of the disclosure may allow for the formation of silicon nitride films with increased etch rate resistance at reduced deposition temperatures. Therefore, the silicon nitride films formed by the methods of the current disclosure may be suitable for lithography/patterning related applications, such as, for example, multiple patterning applications. Therefore, some embodiments of the disclosure may comprise a partially fabricated device structure comprising a masking structure configured for subsequent patterning of an underlying layer, the masking structure comprising a silicon nitride film formed by the methods of the current disclosure. In greater detail and with reference to FIG. 7, a partially fabricated device structure 700 may comprise a substrate 702 configured for subsequent patterning and etching. Disposed over the substrate 702 may be a resist or hard-mask 704 formed by photolithography methods and disposed over the resist or hard-mask 704 may be a silicon nitride film 706 formed by the methods of the current disclosure.

Embodiments of the disclosure may also include a reaction system configured for forming the silicon nitride films of the present disclosure. In more detail, FIG. 8 schematically illustrates a reaction system 800 including a reaction chamber 802 that further includes mechanism for retaining a substrate (not shown) under predetermined pressure, temperature, and ambient conditions, and for selectively exposing the substrate to various gases. A precursor reactant source 804 may be coupled by conduits or other appropriate means 804A to the reaction chamber 802, and may further couple to a manifold, valve control system, mass flow control system, or mechanism to control a gaseous precursor originating from the precursor reactant source 804. A precursor (not shown) supplied by the precursor reactant source 804, the reactant (not shown), may be liquid or solid under room temperature and standard atmospheric pressure conditions. Such a precursor may be vaporized within a reactant source vacuum vessel, which may be maintained at or above a vaporizing temperature within a precursor source chamber. In such embodiments, the vaporized precursor may be transported with a carrier gas (e.g., an inactive or inert gas) and then fed into the reaction chamber 802 through conduit 804A. In other embodiments, the precursor may be a vapor under standard conditions. In such embodiments, the precursor does not need to be vaporized and may not require a carrier gas. For example, in one embodiment the precursor may be stored in a gas cylinder. The reaction system 800 may also include additional precursor reactant sources, such precursor reactant source 806 which may also be couple to the reaction chamber by conduits 806A as described above.

A purge gas source 808 may also be coupled to the reaction chamber 802 via conduits 808A, and selectively supplies various inert or noble gases to the reaction chamber 802 to assist with the removal of precursor gas or waste gasses from the reaction chamber. The various inert or noble gasses that may be supplied may originate from a solid, liquid or stored gaseous form.

The reaction system 800 of FIG. 8, may also comprise a system operation and control mechanism 810 that provides electronic circuitry and mechanical components to selectively operate valves, manifolds, pumps and other equipment included in the reaction system 800. Such circuitry and components operate to introduce precursors, purge gasses from the respective precursor sources 804, 806 and purge gas source 808. The system operation and control mechanism 810 also controls timing of gas pulse sequences, temperature of the substrate and reaction chamber, and pressure of the reaction chamber and various other operations necessary to provide proper operation of the reaction system 800. The operation and control mechanism 810 can include control software and electrically or pneumatically controlled valves to control flow of precursors, reactants and purge gasses into and out of the reaction chamber 402. The control system can include modules such as a software or hardware component, e.g., a FPGA or ASIC, which performs certain tasks. A module can advantageously be configured to reside on the addressable storage medium of the control system and be configured to execute one or more processes.

Those of skill in the relevant arts appreciate that other configurations of the present reaction system are possible, including different number and kind of precursor reactant sources and purge gas sources. Further, such persons will also appreciate that there are many arrangements of valves, conduits, precursor sources, purge gas sources that may be used to accomplish the goal of selectively feeding gases into reaction chamber 802. Further, as a schematic representation of a reaction system, many components have been omitted for simplicity of illustration, and such components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and/or bypasses. In some embodiments, reaction system 800 may include two or more reaction chambers wherein each reaction chamber may be configured for a desired process, for example, a first reaction chamber may be configured for cyclical deposition processes and a second reaction chamber may be configured for plasma processes. In addition, the reaction system 800 may comprise a transfer chamber for transferring substrate(s) from a first reaction chamber to a second reaction chamber under controlled conditions.

The example embodiments of the disclosure described above do not limit the scope of the invention, since these embodiments are merely examples of the embodiments of the invention, which is defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the disclosure, in addition to those shown and described herein, such as alternative useful combination of the elements described, may become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims. 

What is claimed is:
 1. A method for forming a silicon nitride film on a substrate, the method comprising: forming a cyclical silicon nitride film on the substrate by a cyclical deposition process, wherein the cyclical deposition process comprises at least one cycle of: contacting the substrate with a first reactant comprising a silicon halide source, and contacting the substrate with a second reactant comprising a nitrogen source; after the at least one cycle, exposing the cyclical silicon nitride film to a plasma to finish a complete deposition cycle and to form a plasma treated silicon nitride film, wherein the step of exposing renders a surface of the plasma treated silicon nitride film reactive, and wherein a wet etch rate of the plasma treated silicon nitride film is less than a wet etch rate of the cyclical silicon nitride film; after the complete deposition cycle, and thus after forming the plasma treated silicon nitride film, repeating the forming and the exposing steps to perform multiple complete deposition cycles to form multiple plasma treated silicon nitride films; and after repeating the forming and the exposing steps to perform multiple complete deposition cycles; passivating a surface of the plasma treated silicon nitride film, wherein the step of passivating comprises one or more of a plasma process and exposing the plasma treated silicon nitride film to nitrogen (N₂), wherein the step of passivating differs from the step of exposing the cyclical silicon nitride film to the plasma, and wherein the step of passivating reduces a reactivity of a surface of the plasma treated silicon nitride film.
 2. The method of claim 1, wherein the cyclical deposition process is a cyclical atomic layer deposition process.
 3. The method of claim 2, wherein the complete deposition cycle is repeated more than two times prior to the step of passivating.
 4. The method of claim 1, wherein the cyclical deposition process is repeated until the cyclical silicon nitride film has a first desired thickness, wherein repeating the forming and the exposing steps is performed until the multiple plasma treated silicon nitride films has a second desired thickness.
 5. The method of claim 1, wherein the step of passivating comprises contacting the silicon nitride film with nitrogen exposed to a remote plasma prior to removing the silicon nitride film from a semiconductor processing apparatus.
 6. The method of claim 1, further comprising selecting the silicon halide source to comprise at least one of hexaiododisilane (Si₂I₆) or octoiodotrisilane (Si₃I₈).
 7. The method of claim 1, further comprising selecting the nitrogen source to comprise an alkyl-hydrazine.
 8. The method of claim 1, wherein exposing the cyclical silicon nitride film to the plasma comprises exposing the cyclical silicon nitride film to the plasma for a time period of less than approximately 90 seconds.
 9. The method of claim 1, wherein exposing the cyclical silicon nitride film to the plasma comprises exposing the cyclical silicon nitride film to a plasma source comprising at least one of nitrogen (N₂), helium (He), hydrogen (H₂), and argon (Ar).
 10. The method of claim 1, wherein exposing the cyclical silicon nitride film to the plasma comprises exposing the cyclical silicon nitride film to a plasma source comprising helium (He) and nitrogen (N₂).
 11. The method of claim 10, wherein the plasma source comprises a 50%:50% ratio of helium (He) to nitrogen (N₂).
 12. The method of claim 10, wherein the step of passivating comprises contacting the silicon nitride film the nitrogen.
 13. The method of claim 12, wherein the silicon nitride film has an atomic percentage of hydrogen of less than 15%.
 14. The method of claim 1, wherein the silicon nitride film has a wet etch rate in a 2000:1 H₂O:HF solution of approximately less than 5 Angstroms/minute.
 15. The method of claim 1, wherein forming the cyclical silicon nitride film on the substrate by the cyclical deposition process and exposing the cyclical silicon nitride film to the plasma are performed within the same semiconductor processing apparatus.
 16. The method of claim 1, further comprising exposing the substrate to the plasma prior to forming the cyclical silicon nitride film on the substrate by the cyclical deposition process.
 17. The method of claim 1, wherein exposing the cyclical silicon nitride film to the plasma further comprises altering the stress in the cyclical silicon nitride film.
 18. The method of claim 17, wherein altering the stress in the cyclical silicon nitride film further comprises altering the stress from a tensile state to a compressive state.
 19. The method of claim 1, wherein exposing the cyclical silicon nitride film to the plasma further comprises altering a degree of bow in the substrate.
 20. The method of claim 1, wherein the step of passivating comprises contacting the plasma treated silicon nitride film with a nitrogen precursor comprising at least one of ammonia or nitrogen gas plasma prior to removing the silicon nitride film from a semiconductor processing apparatus.
 21. A semiconductor device structure comprising the silicon nitride layer formed by the method of claim
 1. 22. A reaction system configured to perform the method of claim
 1. 